We report a joint photoelectron spectroscopic and theoretical study of the PtZnH5(-) cluster anion. This cluster exhibited an unprecedented planar pentagonal coordination for Pt and an unusual stability and high intensity in the mass spectrum. Both are due to the σ-aromaticity found in the H5-cycle supported by the 5d orbitals on the Pt atom. σ-Aromaticity in all-H systems has been predicted in the past but never found in experimentally observed species. Besides fundamental importance, mixed transition-metal hydrides can be found as intermediates in catalytic processes, and thus, the unexpected stability facilitated by σ-aromaticity can be appreciated also in practical applications.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jz500322n | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Designer Metallic Acceptor-Containing Halogen Bonds: General Strategies.
Chemistry
April 2017
Departments of Chemistry and Material Sciences, Johns Hopkins University, Baltimore, Maryland, MD, 21218, USA.
Being electrostatic interactions in nature, hydrogen bonding (HB) and halogen bonding (XB) are considered to be two parallel worlds. In principle, all the applications that HB have could also be applied to XB. However, there has been no report on an anionic, metallic XB acceptor, but metal anions have been observed to be good HB acceptors.
View Article and Find Full Text PDFσ-Aromaticity in polyhydride complexes of Ru, Ir, Os, and Pt.
Phys Chem Chem Phys
April 2016
Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095-1569, USA. and California NanoSystems Institute, University of California, Los Angeles, CA 90095-1569, USA.
Transition-metal hydrides represent a unique class of compounds, which are essential for catalysis, organic synthesis, and hydrogen storage. In this work we study IrH5(PPh3)2, (RuH5(P(i)Pr3)2)(-), (OsH5(P(i)Pr3)2)(-), and OsH4(PPhMe2)3 polyhydride complexes, inspired by the recent discovery of the σ-aromatic PtZnH5(-) cluster anion. The distinctive feature of these molecules is that, like in the PtZnH5(-) cluster, the metal is five-fold coordinated in-plane, and holds additional ligands at the axial positions.
View Article and Find Full Text PDFPtZnH5(-), A σ-Aromatic Cluster.
J Phys Chem Lett
May 2014
‡Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United States.
We report a joint photoelectron spectroscopic and theoretical study of the PtZnH5(-) cluster anion. This cluster exhibited an unprecedented planar pentagonal coordination for Pt and an unusual stability and high intensity in the mass spectrum. Both are due to the σ-aromaticity found in the H5-cycle supported by the 5d orbitals on the Pt atom.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!